CN111133614A - Silicon-based negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Silicon-based negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN111133614A
CN111133614A CN201980003460.0A CN201980003460A CN111133614A CN 111133614 A CN111133614 A CN 111133614A CN 201980003460 A CN201980003460 A CN 201980003460A CN 111133614 A CN111133614 A CN 111133614A
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silicon
source gas
carbon source
carbon
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CN111133614B (en
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魏良勤
马飞
***
吴玉虎
吴志红
丁晓阳
李凤凤
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Shanghai Shanshan Technology Co Ltd
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/10—Energy storage using batteries

Abstract

The application provides a silicon-based negative electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the silicon-based anode material comprises the following steps: the silicon substrate material is coated with a carbon deposition layer with a certain thickness through vapor deposition gas, the vapor deposition gas comprises a first carbon source gas and a second carbon source gas, the volume percentage of the first carbon source gas and the volume percentage of the second carbon source gas in the vapor deposition gas are increased or decreased in different reaction stages for forming the carbon deposition layer, and the densification degree of one side, close to the silicon substrate material, of the carbon deposition layer is greater than or less than that of the other side of the carbon deposition layer. The coating layer on the surface of the silicon-based negative electrode material prepared by the method has a continuous change junction, so that the cycling stability of the material is greatly improved.

Description

Silicon-based negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The application relates to the field of lithium ion battery materials, in particular to a silicon-based negative electrode material, a preparation method thereof and a lithium ion battery.
Background
The commercial lithium ion battery mainly uses graphite as a negative electrode material, and the theoretical capacity of the graphite is only 372 mA.h/g, so that the demand of the high-energy density lithium ion battery cannot be met. The search for alternative negative electrode materials has been a subject of rapid development of high energy density lithium ion batteries. Among various non-carbon-based anode materials, crystalline silicon is a very promising anode material for lithium ion batteries, and has high theoretical capacity (4200mA · h/g, 9800mA · h/mL) and low delithiation voltage (0.37Vvs. Li/Li +). However, the volume change of crystalline silicon in the charging and discharging process is as high as 310%, and such large expansion and shrinkage causes the existence of large stress in the material, which further causes pulverization of the material, separation of active substances from a current collector and loss of activity, and rapid capacity attenuation, so how to solve the problem of expansion and poor cycle performance of the silicon-based negative electrode material is the key research point of the silicon-based negative electrode material.
In order to solve the above problems, one of the common methods is to uniformly coat a layer of carbon on the outer surface of the silicon particles, so as to obtain a core-shell type silicon-carbon composite material. The presence of the carbon shell reduces direct contact of the silicon surface with the electrolyte and improves electron conduction between the silicon particles, so that the cycling stability of the entire electrode can be greatly improved. In the field of new energy, the carbon deposition layer with a single structure is mainly coated at present.
Disclosure of Invention
The application provides a silicon-based negative electrode material with a structure-change carbon deposition layer on the surface and a preparation method thereof, so as to improve the electrochemical performance of the silicon-based negative electrode material.
One aspect of the present application provides a method for preparing a silicon-based anode material, including: the method comprises the following steps of enabling a silicon substrate material to pass through vapor deposition gas to enable the surface of the silicon substrate material to be coated with a carbon deposition layer with a certain thickness, wherein the vapor deposition gas comprises a first carbon source gas and a second carbon source gas, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are increased or decreased in different reaction stages for forming the carbon deposition layer, and the degree of compaction of the carbon deposition layer close to one side of the silicon substrate material is greater than or less than that of the other side of the carbon deposition layer.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas monotonically increase or decrease during different reaction phases of forming the carbon deposition layer.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased in a stepwise manner at different reaction stages for forming the carbon deposition layer.
In some embodiments, the first carbon source gas is one or a combination of acetylene and ethylene, and the second carbon source gas is one or a combination of benzene and toluene.
In some embodiments, the volume percent of the first carbon source gas and the second carbon source gas in the vapor deposition gas varies from 0 to 20.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased between 0 and 20.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are decreased in a gradient from 5 to 20 to 0 to 5 or increased in a gradient from 0 to 5 to 20.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas monotonically decrease in 3 to 15 steps.
In some embodiments, the method is performed in an inert atmosphere, and the sum of the volumes of the first carbon source gas and the second carbon source gas is 1 to 30% of the total volume of the atmosphere.
In some embodiments, the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx (0 ≦ x ≦ 1.5) and porous silicon, and the median particle size of the silicon substrate material ranges from 1 μm to 20 μm.
In some embodiments, the silicon substrate material further comprises a compound of the formula MSiOy, wherein 0.85 < y ≦ 3; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
In some embodiments, the reaction temperature of the method is 700-1000 ℃, and the reaction time is 3-12 h.
In some embodiments, the carbon deposition layer has a thickness of 10nm to 150 nm.
Another aspect of the present application provides a silicon-based anode material, including: the carbon deposition layer coats the silicon substrate material, wherein the compactness degree of one side, close to the silicon substrate material, of the carbon deposition layer is larger than or smaller than that of the other side of the carbon deposition layer.
In some embodiments, the degree of densification within the carbon deposition layer increases or decreases monotonically from the inner side to the outer side.
In some embodiments, the degree of densification in the carbon deposition layer is increased or decreased in a monotonous manner according to 3 to 15 steps.
In some embodiments, the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx (0 ≦ x ≦ 1.5) and porous silicon, and the median particle size of the silicon substrate material ranges from 1 μm to 20 μm.
In some embodiments, the silicon substrate material further comprises a compound of the formula MSiOy, wherein 0.85 < y ≦ 3; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
In some embodiments, the thickness of the carbon deposition layer is 10 to 150 nm.
In another aspect, the present application provides a lithium ion battery, wherein a negative electrode of the lithium ion battery comprises any one of the silicon-based negative electrode materials described above.
The embodiment of the application provides a silicon-based negative electrode material and a preparation method thereof, aiming at the defects of the existing performance of the silicon-based negative electrode material, a carbon deposition layer with different compactness degrees is formed on the surface of a silicon material by using a chemical vapor deposition method, the part with high structure density in the carbon deposition layer has more stable electrochemical cycle performance, and the part with relatively low density has better interface conductivity.
Further, the chemical vapor deposition process is performed in a vapor deposition furnace having a step temperature and an atmosphere which can be independently controlled, so that the regularity of the densification of the carbon deposition layer can be increased or decreased.
Furthermore, the carbon deposition layer on the surface of the silicon-based negative electrode material has a continuous change structure, and the deposition layer on the inner side is tightly coated, so that the volume effect of the silicon-based negative electrode material in the charge and discharge process can be effectively inhibited, and the interface conductivity is improved; the surface of the outer deposition layer is smooth and compact, which is beneficial to forming a stable SEI (solid electrolyte interphase) film and greatly improving the cycle stability of the material.
In addition, the preparation method of the silicon-based negative electrode material is simple in process, strong in operation continuity, suitable for large-scale industrial production and wide in application prospect in the field of lithium ion batteries.
Additional features of the present application will be set forth in part in the description which follows. The descriptions of the figures and examples below will become apparent to those of ordinary skill in the art from this disclosure. The inventive aspects of the present application can be fully explained by the practice or use of the methods, instrumentalities and combinations set forth in the detailed examples discussed below.
Drawings
The following drawings describe in detail exemplary embodiments disclosed in the present application. Wherein like reference numerals represent similar structures throughout the several views of the drawings. Those of ordinary skill in the art will understand that the present embodiments are non-limiting, exemplary embodiments and that the accompanying drawings are for illustrative and descriptive purposes only and are not intended to limit the scope of the present disclosure, as other embodiments may equally fulfill the inventive intent of the present application. It should be understood that the drawings are not to scale. Wherein:
FIG. 1 is a schematic view of a vapor deposition furnace configuration according to some embodiments of the present application.
Detailed Description
The following description is presented to enable any person skilled in the art to make and use the present disclosure, and is provided in the context of a particular application and its requirements. Various local modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present disclosure. Thus, the present disclosure is not to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
The technical solution of the present application will be described in detail below with reference to the embodiments and the accompanying drawings.
The application provides a preparation method of a silicon-based anode material, which comprises the following steps: the method comprises the following steps of enabling a silicon substrate material to pass through vapor deposition gas to enable the surface of the silicon substrate material to be coated with a carbon deposition layer with a certain thickness, wherein the vapor deposition gas comprises a first carbon source gas and a second carbon source gas, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are increased or decreased in different reaction stages for forming the carbon deposition layer, and the degree of compaction of the carbon deposition layer close to one side of the silicon substrate material is greater than or less than that of the other side of the carbon deposition layer.
In the embodiment of the application, the preparation method of the silicon-based anode material can crush the silicon-based base material into powder particles, and convey the powder particles to the vapor deposition furnace. The silicon substrate material comprises one or more of metallurgical silicon and silicon oxide SiOx (x is more than or equal to 0 and less than or equal to 1.5) and porous silicon, and the median range of the particle size of the silicon substrate material is 1-20 mu m. The silicon substrate material also comprises a compound with the general formula of MSiOy, wherein y is more than 0.85 and less than or equal to 3; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
In the embodiment of the application, the particle size of the silicon substrate material also has a certain influence on the electrochemical performance of the finally formed silicon-based negative electrode material, the particle size of the silicon substrate material is reduced, the specific surface area of the silicon substrate material is increased, the surface reaction accompanying charge and discharge cycles is increased, and more Li + is consumed in the SEI film, so that the cycle characteristic and the first coulombic efficiency of the silicon-based negative electrode material are reduced. The silicon substrate material with increased particle size can prevent active substances in the electrode from being cracked along with charge and discharge to form a new surface, so that the amount of side reaction is reduced, and the cycle performance and the first coulombic efficiency of the silicon substrate material are improved.
When the chemical vapor deposition reaction is carried out in the vapor deposition furnace, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are strongly related to the compactness of the formed carbon deposition layer, the volume percentages of the first carbon source gas and the second carbon source gas are reduced, the compactness of the formed carbon deposition layer is increased, the expansion effect of the carbon deposition layer on an internal nuclear structure is more obvious, the electrochemical cycle performance of the silicon-based negative electrode material is improved, and the carbon deposition layer with a smooth and compact surface is favorable for forming a stable SEI film and improving the first coulomb efficiency of the silicon-based negative electrode material; the volume percentages of the first carbon source gas and the second carbon source gas are increased, the densification of the formed carbon deposition layer is reduced, and the interfacial conductivity of the carbon deposition layer is increased. In some embodiments, the first carbon source gas is one or a combination of acetylene and ethylene, and the second carbon source gas is one or a combination of benzene and toluene.
In some embodiments of the present application, the volume percentages of the first carbon source gas and the second carbon source gas may be increased or decreased in different reaction stages to adjust the densification profile of the carbon deposition layer when performing the chemical vapor deposition reaction. For example, the volume percentages of the first carbon source gas and the second carbon source gas may be increased in stages, then decreased in stages, and then increased in stages, so that carbon deposition layers having alternately-distributed degrees of densification may be formed. In an embodiment of the present application, the volume percentage of the first carbon source gas and the second carbon source gas in the vapor deposition gas is increased or decreased between 0 and 20.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas monotonically increase or decrease during different reaction phases of forming the carbon deposition layer. That is, the volume percentages of the first carbon source gas and the second carbon source gas are adjusted continuously or intermittently according to settings for forming a carbon deposition layer in which the degree of densification is continuously increased or is increased abruptly, or a carbon deposition layer in which the degree of densification is continuously decreased or is decreased abruptly. For example, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased between 0 and 20.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased in a stepwise manner at different reaction stages for forming the carbon deposition layer. The degree of densification of the formed carbon deposition layer is also increased or decreased in a stepwise manner. For example, the volume percentage of the first carbon source gas and the second carbon source gas in the vapor deposition gas is reduced from 5 to 20 to 0 to 5 in a gradient manner or increased from 0 to 5 to 20 in a gradient manner. Optionally, in some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas monotonically decrease in 3 to 15 steps.
The change of the degree of compactness of the carbon deposition layer also affects the electrochemical performance of the silicon-based negative electrode material. The carbon deposition layer structure comprises a certain number of layers due to the change of the compactness of the carbon deposition layer, the number of times of the volume percentage change of the first carbon source gas and the second carbon source gas is increased, the number of layers of the carbon deposition layer structure is increased, and the cycle performance of the silicon-based negative electrode material is better.
When the variation value of the volume percentages of the first carbon source gas and the second carbon source gas is larger, the structural hierarchy of the formed carbon deposition layer is more obvious. Optionally, the carbon deposition layer structure includes 3 to 15 layers, and the thickness of each layer is the same or similar.
FIG. 1 is a schematic view of a vapor deposition furnace configuration according to some embodiments of the present application. As shown in fig. 1, the silicon substrate material is pulverized into powder particles, and the powder particles are transported through a feed zone to an elevated temperature zone of a vapor deposition furnace. The powder particles are heated in an elevated temperature zone to a first temperature, for example 700 ℃ to 1000 ℃. After the temperature is raised, the powder particles are conveyed to a heat preservation area. The heat preservation zone is provided with n sections of reaction zones capable of independently controlling atmosphere, such as a 1 st hearth zone, a 2 nd hearth zone, a 3 rd hearth zone, a 4 th hearth zone, a. The different reaction areas correspond to different reaction stages in the carbon deposition layer formation process. In some embodiments, the holding section may be equally or unequally divided into n sections by distance. The value of n is, for example, 3 to 15.
For each reaction region, the atmosphere may include a first carbon source gas (corresponding to carbon source a in fig. 1), a second carbon source gas (corresponding to carbon source B in fig. 1), and an inert gas. The first carbon source gas can be one or two of acetylene and ethylene. The second carbon source gas may be one or a combination of benzene and toluene. The inert gas may be one or a combination of at least two of argon, nitrogen and helium. The total volume of the first carbon source gas and the second carbon source gas accounts for 1-30% of the total volume percentage of the atmosphere.
The volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are increased or decreased in different reaction stages for forming the carbon deposition layer. And recording the volume ratio of the first carbon source gas to the second carbon source gas in the total atmosphere volume of each section of the heat preservation area as R, and then decreasing or increasing the R from the R1 of the 1 st furnace area to the Rn of the n-th furnace area according to requirements. For example, R1 for the 1 st furnace zone is 19, R2 for the 2 nd furnace zone is 17, R3 for the 3 rd furnace zone is 14, R4 for the 4 th furnace zone is 12, R5 for the 5 th furnace zone is 8, and R6 for the 6 th furnace zone is 6.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas monotonically increase or decrease during different reaction phases of forming the carbon deposition layer. The volume percentages of the first carbon source gas and the second carbon source gas may be increased or decreased monotonically between 0 and 20. For example, R1 for the 1 st furnace zone is 15, R2 for the 2 nd furnace zone is 12, R3 for the 3 rd furnace zone is 9, R4 for the 4 th furnace zone is 6, and so on. For another example, R1 for the 1 st furnace zone is 6, R2 for the 2 nd furnace zone is 9, R3 for the 3 rd furnace zone is 12, R4 for the 4 th furnace zone is 15, and so on.
In some embodiments, the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased in a stepwise manner at different reaction stages for forming the carbon deposition layer. The volume percentage of the first carbon source gas and the second carbon source gas is changed between 0 and 20, namely R is more than 0 and less than 20. For example: the volume percentage of the first carbon source gas and the second carbon source gas in the vapor deposition gas can be reduced from 5 to 20 to 0 to 5 in a gradient manner or increased from 0 to 5 to 20 in a gradient manner. The volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically decreased according to 3-15 steps. Since the soak zone may be divided into a plurality of reaction zones (e.g., 3 to 15) in which the atmosphere can be independently controlled, the volume percentages of the first carbon source gas and the second carbon source gas may be considered to be uniform and constant in the same reaction zone, and may be monotonically increased or decreased between different reaction zones. For example, R1 for the 1 st furnace zone is 15, R2 for the 2 nd furnace zone is 12, R3 for the 3 rd furnace zone is 9, R4 for the 4 th furnace zone is 6, and so on. For another example, R1 for the 1 st furnace zone is 6, R2 for the 2 nd furnace zone is 9, R3 for the 3 rd furnace zone is 12, R4 for the 4 th furnace zone is 15, and so on.
The vapor deposition heat treatment temperature of the heat preservation area is 700-1000 ℃, and the time is 3-12 h. And after the powder material is coated by vapor deposition, cooling to room temperature under the condition of inert gas to obtain the silicon-based negative electrode material with the surface provided with the carbon deposition layer with the structural change. The thickness of the carbon deposition layer may be 10nm to 150 nm.
The preparation of silicon material with the surface coated by the carbon deposition layer with structural change is realized by utilizing chemical vapor deposition reaction and controlling the heat treatment time of reactants under different atmosphere conditions by adjusting the sectional atmosphere conditions of the vapor deposition reaction furnace. The carbon deposition layer is tightly coated, so that the volume effect and the conductivity of the silicon-based negative electrode material in the charge and discharge process of the battery are effectively inhibited, and the cycling stability of the material is greatly improved.
The embodiment of the application also provides a silicon-based anode material prepared by the preparation method of the silicon-based anode material. Since the gas composition changes stepwise during the vapor deposition process, the carbon deposition layer formed also has structural changes. The application provides a silicon-based negative electrode material includes silicon substrate material and carbon deposit layer, carbon deposit layer cladding silicon substrate material, wherein, carbon deposit layer is close to the degree of compactness of silicon substrate material one side is greater than/is less than the opposite side of carbon deposit layer. The silicon substrate material comprises one or a mixture of more of metallurgical silicon, silicon oxide SiOx (x is more than or equal to 0 and less than or equal to 1.5) and porous silicon, and the median range of the particle size of the silicon substrate material is 1-20 mu m.
In some embodiments, the degree of densification within the carbon deposition layer increases or decreases monotonically from the inner side to the outer side. Since the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are increased or decreased at different reaction stages for forming the carbon deposition layer, the carbon deposition layer is formed to be densified differently at different gas volume ratios. The degree of densification of the carbon deposition layer may increase or decrease from the inner side to the outer side according to the volume percentage of the first carbon source gas and the second carbon source gas.
In some embodiments, the degree of densification within the carbon deposition layer monotonically increases or decreases in 3-15 steps. Since the soak zone may be divided into a plurality of reaction zones (e.g., 3 to 15) in which the atmosphere can be independently controlled, the volume percentages of the first carbon source gas and the second carbon source gas may be considered uniform and constant in the same reaction zone, and may be monotonically increased or decreased between different reaction zones, the degree of density of the carbon deposition layer formed in the same reaction zone may be considered substantially constant or slightly varied, and the degree of density of the carbon deposition layer formed in different reaction zones may be considered as a trend of increasing or decreasing.
The present application is discussed in more detail below in connection with examples 1-6.
Example 1
(1) The silicon oxide SiO particles were mechanically ground to D50 ═ 8 μm.
(2) And (2) putting the powder obtained in the step (1) into a vapor deposition furnace for vapor deposition coating treatment. The heat-preserving zone of the vapor deposition furnace is provided with 12 sections of zones capable of independently controlling the atmosphere, and the atmosphere condition is mixed gas of argon, ethylene and benzene. Ethylene and benzene were vapor deposition gases, the sum of the volumes of which accounted for 8% of the total gas volume introduced (the total gas volume being the sum of the volumes of argon, ethylene, and benzene). The atmosphere composition and the corresponding R value of the furnace in the 12 sections of the holding zone are shown in Table 1. The vapor deposition temperature is 950 ℃, and the axial speed of the material is adjusted, so that the time for the powder to pass through the heat preservation area is 6 hours. And (3) after the sample is coated by vapor deposition, cooling to room temperature under the condition of nitrogen to obtain the silicon-based negative electrode material with the carbon deposition layer with the continuous structural change on the surface.
TABLE 1
Figure BDA0002358703060000131
Example 2
(1) The silicon oxide SiO particles were mechanically ground to D50 ═ 8 μm.
(2) And (2) putting the powder obtained in the step (1) into a vapor deposition furnace for vapor deposition coating treatment. The heat-preserving zone of the vapor deposition furnace is provided with 12 sections of zones capable of independently controlling the atmosphere, and the atmosphere condition is mixed gas of argon, ethylene and toluene. Ethylene and toluene were the vapor deposition gases, the sum of the two volumes accounting for 10% of the total gas volume fed in. The atmosphere composition and the corresponding R value of the furnace in the 12 sections of the holding zone are shown in Table 2. The vapor deposition temperature is 950 ℃, and the axial speed of the material is adjusted, so that the time for the powder to pass through the heat preservation area is 6 hours. And (3) after the sample is coated by vapor deposition, cooling to room temperature under the condition of nitrogen to obtain the silicon-based negative electrode material with the carbon deposition layer with the continuous structural change on the surface.
TABLE 2
Figure BDA0002358703060000132
Figure BDA0002358703060000141
Example 3
(1) The silicon oxide SiO particles were mechanically ground to D50 ═ 8 μm.
(2) And (2) putting the powder obtained in the step (1) into a vapor deposition furnace for vapor deposition coating treatment. The heat-preserving zone of the vapor deposition furnace is provided with 12 sections of zones capable of independently controlling atmosphere, and the atmosphere condition is mixed gas of argon, acetylene and benzene. Acetylene and benzene are vapor deposition gases, and the sum of the volumes of the acetylene and the benzene accounts for 10 percent of the total volume of the introduced gas. The atmosphere composition and the corresponding R value of the furnace in the 12 sections of the holding zone are shown in Table 3. The vapor deposition temperature is 950 ℃, and the axial speed of the material is adjusted, so that the time for the powder to pass through the heat preservation area is 6 hours. And (3) after the sample is coated by vapor deposition, cooling to room temperature under the condition of nitrogen to obtain the silicon-based negative electrode material with the carbon deposition layer with the continuous structural change on the surface.
TABLE 3
Figure BDA0002358703060000142
Example 4
(1) Metallurgical silicon particles were milled by gas stream milling to a D50 of 2.5 μm.
(2) And (2) putting the powder obtained in the step (1) into a vapor deposition furnace for vapor deposition coating treatment. The heat-preserving zone of the vapor deposition furnace is provided with 12 sections of zones capable of independently controlling the atmosphere, and the atmosphere condition is mixed gas of argon, ethylene and benzene. Ethylene and benzene were vapor deposition gases, the sum of the two volumes accounting for 16% of the total gas volume introduced. The atmosphere composition and the corresponding R value of the furnace in the 12 sections of the holding zone are shown in Table 4. The vapor deposition temperature is 850 ℃, and the axial speed of the material is adjusted, so that the time for the powder to pass through the heat preservation area is 6 hours. And (3) after the sample is coated by vapor deposition, cooling to room temperature under the condition of nitrogen to obtain the silicon-based negative electrode material with the carbon deposition layer with the continuous structural change on the surface.
TABLE 4
Figure BDA0002358703060000151
Example 5
(1) Metallurgical silicon particles were milled by gas stream milling to a D50 of 2.5 μm.
(2) And (2) putting the powder obtained in the step (1) into a vapor deposition furnace for vapor deposition coating treatment. The heat-preserving zone of the vapor deposition furnace is provided with 12 sections of zones capable of independently controlling the atmosphere, and the atmosphere condition is mixed gas of argon, ethylene and benzene. Ethylene and benzene were vapor deposition gases, the sum of the two volumes accounting for 16% of the total gas volume introduced. The atmosphere composition and the corresponding R value of the furnace in the 12 sections of the holding zone are shown in Table 3. The vapor deposition temperature is 850 ℃, and the axial speed of the material is adjusted, so that the time for the powder to pass through the heat preservation area is 6 hours. And (3) after the sample is coated by vapor deposition, cooling to room temperature under the condition of nitrogen to obtain the silicon-based negative electrode material with the carbon deposition layer with the continuous structural change on the surface.
TABLE 5
Figure BDA0002358703060000161
Example 6
(1) Metallurgical silicon particles were milled by gas stream milling to a D50 of 2.5 μm.
(2) And (2) putting the powder obtained in the step (1) into a vapor deposition furnace for vapor deposition coating treatment. The heat-preserving zone of the vapor deposition furnace is provided with 12 sections of zones capable of independently controlling atmosphere, and the atmosphere condition is mixed gas of argon, acetylene and benzene. Acetylene and benzene are vapor deposition gases, and the sum of the volumes of the acetylene and the benzene accounts for 10 percent of the total volume of the introduced gas. The atmosphere composition and the corresponding R value of the furnace in the 12 sections of the holding zone are shown in Table 3. The vapor deposition temperature is 850 ℃, and the axial speed of the material is adjusted, so that the time for the powder to pass through the heat preservation area is 6 hours. And (3) after the sample is coated by vapor deposition, cooling to room temperature under the condition of nitrogen to obtain the silicon-based negative electrode material with the carbon deposition layer with the continuous structural change on the surface.
TABLE 6
Figure BDA0002358703060000162
The samples of the silicon-based negative electrode materials obtained in the above examples 1 to 6 were prepared into button cells by using lithium sheets as counter electrodes, and were subjected to charge cycle tests, wherein the charge-discharge rate was 0.1C, and the charge-discharge voltage range was 0.01V to 1.5.0V. The test results obtained are shown in table 7.
TABLE 7
Sample numbering Specific first cycle discharge capacity First week coulombic efficiency Retention of 10-week cycle capacity
Example 1 1660.1 76.3％ 78.4％
Example 2 1645.4 76.7％ 80.9％
Examples3 1670.3 77.5％ 71.5％
Example 4 1464.3 74.6％ 68.8％
Example 5 1476.8 74.3％ 64.7％
Example 6 1512.4 73.5％ 57.6％
It can be seen from the test data in table 7 that, in embodiments 1 to 3, the volume percentages of the first carbon source gas and the second carbon source gas are sequentially reduced, so that the density of the formed carbon deposition layer is sequentially increased, the expansion effect of the carbon deposition layer for inhibiting the internal core structure is more obvious, the improvement of the cycle performance is facilitated, and the carbon deposition layer with the smooth and dense surface is beneficial to forming a stable SEI film and improving the first coulombic efficiency.
Moreover, in example 2, as the number of structural levels of the carbon deposition layer increases, the cycle performance of the silicon-based anode material is better. In the embodiment 3, the benzene volume percentage content of the whole second carbon source gas is more, so that a smooth and densified carbon deposition layer is formed, and the formation of an SEI film is facilitated, so that the coulombic efficiency is improved to a certain extent for the first time, but the structural hierarchy of the carbon deposition layer is less, and the cycle performance of the carbon deposition layer is reduced compared with that of the embodiment 2; example 1 the carbon content and the number of carbon deposition layers were slightly reduced compared to example 2, so the capacity was improved, but the cycle was slightly reduced.
In examples 5 to 6, the cycle performance of the silicon-based negative electrode material was reduced compared to examples 1 to 3, mainly due to the change in the median particle size of the silicon-based base material particles. When the median diameter of the negative active material particles is 2.5 μm, the specific surface area thereof increases, and thus the surface reaction accompanying charge and discharge cycles increases, and more Li + is consumed to form an SEI film, thereby reducing cycle characteristics and first coulombic efficiency. When the median particle diameter is 8 μm, the active material is prevented from being broken with charge and discharge, and a new surface is not easily generated, so that the amount of side reactions is reduced, and the cycle performance and the first coulombic efficiency are excellent. Comparing examples 5 and 6, the number of carbon structure layers in example 5 is greater than that in example 6, and the cycle performance is improved; in example 6, since the median particle diameter of the silicon-based material is 2.5 microns, the specific surface area is large, the carbon content is low due to the fact that 10% of volume fraction carbon source is coated, and the cycle performance and the first coulombic efficiency are low due to the fact that the number of carbon structural layers is small; however, the capacity is improved correspondingly because the Si/C ratio is relatively high compared with examples 4 and 5.
In conclusion, upon reading the present detailed disclosure, those skilled in the art will appreciate that the foregoing detailed disclosure can be presented by way of example only, and not limitation. Those skilled in the art will appreciate that the present application is intended to cover various reasonable variations, adaptations, and modifications of the embodiments described herein, although not explicitly described herein. Such alterations, improvements, and modifications are intended to be suggested by this disclosure, and are within the spirit and scope of the exemplary embodiments of this disclosure.
It is to be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It will be further understood that, although the terms first, second, third, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. Thus, a first element in some embodiments may be termed a second element in other embodiments without departing from the teachings of the present application. The same reference numerals or the same reference identifiers denote the same elements throughout the specification.
Further, exemplary embodiments are described by referring to cross-sectional illustrations and/or plan illustrations that are idealized exemplary illustrations.

Claims (20)

1. A preparation method of a silicon-based anode material comprises the following steps:
coating a carbon deposition layer with a certain thickness on the surface of a silicon substrate material by passing the silicon substrate material through vapor deposition gas, wherein the vapor deposition gas comprises a first carbon source gas and a second carbon source gas,
the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are increased or decreased in different reaction stages for forming a carbon deposition layer, and the densification degree of one side of the carbon deposition layer close to the silicon substrate material is greater than or less than that of the other side of the carbon deposition layer.
2. The method of claim 1, wherein the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas monotonically increase or decrease during different reaction phases for forming a carbon deposition layer.
3. The method for preparing a silicon-based anode material according to claim 1, wherein the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased in a stepwise manner in different reaction stages for forming a carbon deposition layer.
4. The method for preparing the silicon-based anode material according to any one of claims 1 to 3, wherein the first carbon source gas is one or a combination of acetylene and ethylene, and the second carbon source gas is one or a combination of benzene and toluene.
5. The method for preparing a silicon-based anode material according to claim 1, wherein the volume percentage of the first carbon source gas and the second carbon source gas in the vapor deposition gas varies from 0 to 20.
6. The method for preparing the silicon-based anode material of claim 1, wherein the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically increased or decreased between 0 and 20.
7. The method for preparing a silicon-based anode material according to claim 1, wherein the volume percentage of the first carbon source gas and the second carbon source gas in the vapor deposition gas is gradually decreased from 5 to 20 to 0 to 5 or gradually increased from 0 to 5 to 20.
8. The method for preparing a silicon-based anode material according to claim 1, wherein the volume percentages of the first carbon source gas and the second carbon source gas in the vapor deposition gas are monotonically decreased in 3 to 15 steps.
9. The method for preparing the silicon-based anode material of claim 1, wherein the method is carried out in an inert atmosphere, and the volume sum of the first carbon source gas and the second carbon source gas accounts for 1-30% of the total volume of the atmosphere.
10. The method for preparing a silicon-based anode material as claimed in claim 1, wherein the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx (0. ltoreq. x. ltoreq.1.5) and porous silicon, and the median particle size of the silicon substrate material is in a range of 1 μm to 20 μm.
11. The method for preparing a silicon-based anode material according to claim 10, wherein the silicon substrate material further comprises a compound having a general formula of MSiOy, wherein y is more than 0.85 and less than or equal to 3; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
12. The preparation method of the silicon-based anode material as claimed in claim 1, wherein the reaction temperature of the method is 700-1000 ℃, and the reaction time is 3-12 h.
13. The method for preparing a silicon-based anode material according to claim 1, wherein the carbon deposition layer has a thickness of 10nm to 150 nm.
14. A silicon-based anode material comprising:
a silicon base material; and
and the carbon deposition layer coats the silicon substrate material, wherein the compactness of one side of the carbon deposition layer close to the silicon substrate material is greater than or less than that of the other side of the carbon deposition layer.
15. The silicon-based anode material of claim 14, wherein the degree of densification in the carbon deposition layer monotonically increases or decreases from the inner side to the outer side.
16. The silicon-based anode material as claimed in claim 14, wherein the degree of densification in the carbon deposition layer is monotonically increased or decreased in 3 to 15 steps.
17. The silicon-based negative electrode material as claimed in claim 14, wherein the silicon-based material comprises one or more of metallurgical silicon, silicon oxide SiOx (0. ltoreq. x.ltoreq.1.5) and porous silicon, and the median particle size of the silicon-based material is in the range of 1 μm to 20 μm.
18. The silicon-based anode material of claim 14, wherein the silicon-based substrate material further comprises a compound having the formula MSiOy, wherein y is greater than 0.85 and less than or equal to 3; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
19. The silicon-based anode material of claim 14, wherein the carbon deposition layer has a thickness of 10nm to 150 nm.
20. A lithium ion battery, characterized in that the negative electrode of the lithium ion battery comprises the silicon-based negative electrode material according to any one of claims 14 to 19.
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